High-voltage devices

ABSTRACT

The present disclosure provides supercapacitors that may avoid the shortcomings of current energy storage technology. Provided herein are supercapacitor devices, and methods of fabrication thereof comprising the manufacture or synthesis of an active material on a current collector and/or the manufacture of supercapacitor electrodes to form planar and stacked arrays of supercapacitor electrodes and devices. Prototype supercapacitors disclosed herein may exhibit improved performance compared to commercial supercapacitors. Additionally, the present disclosure provides a simple, yet versatile technique for the fabrication of supercapacitors through masking and etching.

CROSS-REFERENCE

This application is a continuation of U.S. application Ser. No.15/410,404, filed Jan. 19, 2017, which claims the benefit of U.S.Provisional Application No. 62/286,126, filed Jan. 22, 2016, whichapplications are incorporated herein by reference in their entireties.

BACKGROUND

The development of high performance energy storage devices has gainedsignificant attention in a broad range of applications. While normalelectronic devices progress rapidly, according to Moore's law, batterieshave advanced only slightly, mainly due to the limitations of currentmaterials' energy densities and capacities.

SUMMARY

The inventors have identified that batteries with a reduced charge timeand an increased charge density have a profound effect on the design anduse of portable electronics and renewable energy devices. Providedherein are methods, devices and systems of supercapacitors. The methodsmay include the manufacture (or synthesis) of an active material on acurrent collector and/or the manufacture of supercapacitor electrodes.Some embodiments provide methods, devices and systems for themanufacture (or synthesis) of planar and stacked arrays of electrodesand/or for the manufacture (or synthesis) of supercapacitors.

A first aspect of the disclosure provided herein is supercapacitordevice comprising an array of electrodes, wherein each electrodecomprises a current collector; and an active material on a portion offirst surface of the current collector.

In some embodiments, the supercapacitor of the first aspect furthercomprises the active material on a portion of a second surface of thecurrent collector.

In some embodiments, each electrode in the array is separated from asubsequent electrode by a gap.

In some embodiments, the current collector comprises a metal film or apolymeric film or any combination thereof, wherein the metal filmcomprises silver, copper, gold, aluminum, calcium, tungsten, zinc,tungsten, brass, bronze, nickel, lithium, iron, platinum, tin, carbonsteel, lead, titanium, stainless steel, mercury, chromium, galliumarsenide or any combination thereof, and wherein the polymeric filmcomprises polyfluorene, polyphenylene, polypyrene, polyazulene,polynaphthalene, polyacetylene, poly p-phenylene vinylene, polypyrrole,polycarbazole, polyindole, polyazepinem, polyaniline, polythiophene,poly 3,4-ethylenedioxythiophene, poly p-phenylene sulfide,polyacetylene, poly p-phenylene vinylene or any combination thereof.

In some embodiments, the active material comprises two or more separatedand interconnected layers. In some embodiments, the active materialcomprises carbon, activated carbon, graphene, polyaniline,polythiophene, an interconnected corrugated carbon-based network (ICCN)or any combination thereof. In some embodiments, the active material hasa surface density of from about 250 meters squared per gram to about3,500 meters squared per gram. In some embodiments, the active materialhas a conductivity of from about 750 siemens/meter to about 3,000siemens/meter.

In some embodiments, the array of electrodes is a planar array ofelectrodes. In further such embodiments, the electrolyte is aqueouswherein the number of electrodes is about 5, and the produced voltagepotential across the array of electrodes is from about 2.5 V to about 10V.

In further such embodiments, the electrolyte comprises tetraethylammonium tetrafluoroborate (TEABF₄) in acetonitrile wherein the numberof electrodes is about 5, and the voltage potential produced across thearray of electrodes is from about 6 V to about 24 V. In further suchembodiments, the electrolyte is aqueous, wherein the number ofelectrodes is about 180, and the voltage potential produced across thearray of electrodes is from about 100 V to about 360 V. In further suchembodiments the electrolyte comprises tetraethyl ammoniumtetrafluoroborate (TEABF₄) in acetonitrile, wherein the number ofelectrodes is about 72, and the voltage potential produced across thearray of electrodes is from about 100 V to about 360 V.

In some embodiments, the array of electrodes is a stacked array ofelectrodes.

In some embodiments, the supercapacitor device of the first aspectfurther comprises at least one or more of a separator and a support,wherein the at least one or more of a separator and a support ispositioned between a pair of adjacent electrodes.

In some embodiments, the supercapacitor device of the first aspectfurther comprises an electrolyte, wherein the electrolyte is a liquid, asolid, a gel, or any combination thereof comprising a polymer, silica,fumed silica, fumed silica nano-powder, 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, phosphoric acid, tetraethyl ammoniumtetrafluoroborate (TEABF₄), acetonitrile,1-ethyl-3-methylimidazoliumtetrafluoroborate, ethanolammonium nitrate, adicarboxylate, a prostaglandin, adenosine monophosphate, guanosinemonophosphate, a p-aminohippurate, polysiloxane, polyphosphazene,potassium hydroxide, polyvinyl alcohol or any combination thereof.

A second aspect of the disclosure provided herein is a method offabricating a supercapacitor comprising, fabricating an array ofelectrodes comprising: applying an active material onto a portion of thefirst surface of the current collector; and drying the active materialon the current collector, wherein each electrode is separated from asubsequent electrode by a gap.

In some embodiments, the method of the second aspect further comprisesapplying an active material onto a portion of the second surface of thecurrent collector; and drying the active material on the currentcollector.

In some embodiments, at least one or more of a tape and a mask, shieldsa portion of the substrate to thereby prevent application of an activematerial onto the shielded portion of the substrate.

In some embodiments, the active material is applied in the form of aslurry. In some embodiments, the slurry is applied to the substrate by adoctor blade. In some embodiments, the process of applying an activematerial onto the first surface of the current collector and the processof applying an active material onto the second surface of the currentcollector are performed simultaneously.

In some embodiments, the drying of the active material on the currentcollector occurs at a temperature of from about 40° C. to about 160° C.In some embodiments, the drying of the active material on the currentcollector current collector occurs over a period of time from about 6hours to about 24 hours.

In some embodiments, the electrode array comprises a planar electrodearray. In some embodiments, planar electrode array is fabricated byetching or cutting the active material and the current collector.

In some embodiments, the electrode array comprises a stacked electrodearray.

In some embodiments, the method of the second aspect further comprisespositioning at least one or more of a separator and a support, between apair of consecutive electrodes.

In some embodiments, the method of the second aspect further comprisesdispersing an electrolyte on the array of electrodes; encasing the arrayof electrodes in a sheath; and inserting the encased array of electrodesinto a housing.

In some embodiments, the electrolyte is a liquid, a solid, a gel, or anycombination thereof comprising a polymer, silica, fumed silica, fumedsilica nano-powder, 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, phosphoric acid, tetraethyl ammoniumtetrafluoroborate (TEABF₄), acetonitrile,1-ethyl-3-methylimidazoliumtetrafluoroborate, ethanolammonium nitrate, adicarboxylate, a prostaglandin, adenosine monophosphate, guanosinemonophosphate, a p-aminohippurate, polysiloxane, polyphosphazene,potassium hydroxide, polyvinyl alcohol or any combination thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The novel features of the disclosure are set forth with particularity inthe appended claims. A better understanding of the features andadvantages of the present disclosure will be obtained by reference tothe following detailed description that sets forth illustrativeembodiments, in which the principles of the disclosure are utilized, andthe accompanying drawings or figures (also “FIG.” and “FIGs.” herein),of which:

FIGS. 1A-D show exemplary illustrations of supercapacitors havingmultiple electrodes.

FIG. 2 shows an exemplary illustration of a supercapacitor having 180cells.

FIGS. 3A-B show exemplary illustrations of a single-sided electrode anda double-sided electrode.

FIGS. 4A-B show exemplary front and top cross-sectional illustrations ofan assembled supercapacitor.

FIGS. 5A-B show an exemplary front cross-sectional illustration of anassembled supercapacitor with supports, and an exemplary illustration ofa supported double-sided electrode.

FIGS. 6A-C show exemplary exploded, perspective and top viewillustrations of a packaged single-cell supercapacitor.

FIG. 7 shows an exemplary image of the application of an active materialonto a current collector.

FIG. 8 shows an exemplary image of the active material applied on thecurrent collector.

FIGS. 9A-B show exemplary images of the electrode after drying and taperemoval.

FIG. 10 shows an exemplary image of the fabrication of a patternedplanar electrode.

FIG. 11 shows an exemplary image of a high-voltage supercapacitor duringelectrochemical testing.

FIGS. 12A-E show cyclic voltammetry (CV) graphs of an exemplarysupercapacitor device at different scan rates.

FIG. 13 shows an overlay of the cyclic voltammetry (CV) graphs of anexemplary supercapacitor device at different scan rates.

FIG. 14 shows the charge and discharge performance of an exemplarysupercapacitor under a constant current.

FIG. 15 shows the Warburg impedance of an exemplary supercapacitor.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have recognized a need for an improved design of, and theintegration of hybrid materials into, microsupercapacitors, to simplifythe microfabrication of 3D microelectrodes with micrometer separations.

The present disclosure provides a simple, yet versatile technique forthe fabrication of supercapacitors. The present disclosure provides amethod for the preparation and/or integration of supercapacitors forhigh voltage applications. In some embodiments, the present disclosureprovides a method for the direct preparation and integration ofsupercapacitors for high voltage applications. The supercapacitors maycomprise an array of separate electrochemical cells. In someembodiments, the array of separate electrochemical electrodes may bedirectly fabricated in the same plane and in one step. Thisconfiguration may provide very good control over the voltage and currentoutput. In some embodiments, the array may be integrated with solarelectrodes for efficient solar energy harvesting and storage. In someembodiments, the devices are integrated supercapacitors for high voltageapplications.

An aspect of the disclosure provides a supercapacitor device comprisingan array of electrodes, wherein each electrode comprises a currentcollector; and an active material on a portion of first surface of thecurrent collector. In some embodiments, the current collector comprisesactive material on a portion of a second surface of the currentcollector. In some embodiments, an electrode in the array is separatedfrom a subsequent electrode by a gap.

In some embodiments, the active material comprises carbon, activatedcarbon, graphene, polyaniline, polythiophene, an interconnectedcorrugated carbon-based network (ICCN) or any combination thereof.

In some embodiments, the current collector comprises a metal film or apolymeric film or any combination thereof. In some embodiments, themetal film comprises silver, copper, gold, aluminum, calcium, tungsten,zinc, tungsten, brass, bronze, nickel, lithium, iron, platinum, tin,carbon steel, lead, titanium, stainless steel, mercury, chromium,gallium arsenide or any combination thereof. In some embodiments, thepolymeric film comprises polyfluorene, polyphenylene, polypyrene,polyazulene, polynaphthalene, polyacetylene, poly p-phenylene vinylene,polypyrrole, polycarbazole, polyindole, polyazepinem, polyaniline,polythiophene, poly 3,4-ethylenedioxythiophene, poly p-phenylenesulfide, polyacetylene, poly p-phenylene vinylene or any combinationthereof.

In some embodiments, the thickness of the current collector is fromabout 50 nanometers to about 200 nanometers. In some embodiments, thethickness of the current collector is at least about 50 nanometers. Insome embodiments, the thickness of the current collector is at mostabout 200 nanometers. In some embodiments, thickness of the currentcollector is about 50 nanometers to about 75 nanometers, about 50nanometers to about 100 nanometers, about 50 nanometers to about 125nanometers, about 50 nanometers to about 150 nanometers, about 50nanometers to about 175 nanometers, about 50 nanometers to about 200nanometers, about 75 nanometers to about 100 nanometers, about 75nanometers to about 125 nanometers, about 75 nanometers to about 150nanometers, about 75 nanometers to about 175 nanometers, about 75nanometers to about 200 nanometers, about 100 nanometers to about 125nanometers, about 100 nanometers to about 150 nanometers, about 100nanometers to about 175 nanometers, about 100 nanometers to about 200nanometers, about 125 nanometers to about 150 nanometers, about 125nanometers to about 175 nanometers, about 125 nanometers to about 200nanometers, about 150 nanometers to about 175 nanometers, about 150nanometers to about 200 nanometers, or about 175 nanometers to about 200nanometers.

In some embodiments, the active material comprises two or more separatedand interconnected layers. In some embodiments, a layer is corrugated.In some embodiments, a layer is one atom thick.

In some embodiments, a portion of the layers are separated by a distanceof at least about 1 nanometer (nm). In some embodiments, a portion ofthe layers are separated by a distance of at most about 150 nm. In someembodiments, a portion of the layers are separated by a distance ofabout 1 nm to about 150 nm. In some embodiments, a portion of the layersare separated by a distance of about 1 nm to about 5 nm, about 1 nm toabout 10 nm, about 1 nm to about 25 nm, about 1 nm to about 50 nm, about1 nm to about 100 nm, about 1 nm to about 150 nm, about 5 nm to about 10nm, about 5 nm to about 25 nm, about 5 nm to about 50 nm, about 5 nm toabout 100 nm, about 5 nm to about 150 nm, about 10 nm to about 25 nm,about 10 nm to about 50 nm, about 10 nm to about 100 nm, about 10 nm toabout 150 nm, about 25 nm to about 50 nm, about 25 nm to about 100 nm,about 25 nm to about 150 nm, about 50 nm to about 100 nm, about 50 nm toabout 150 nm, or about 100 nm to about 150 nm.

In some embodiments, the active material has a surface density of atleast about 250 meters squared per gram (m²/g). In some embodiments, theactive material has a surface density of at most about 3,500 m²/g. Insome embodiments, the active material has a surface density of about 250m²/g to about 3,500 m²/g. In some embodiments, the active material has asurface density of about 250 m²/g to about 500 m²/g, about 250 m²/g toabout 750 m²/g, about 250 m²/g to about 1,000 m²/g, about 250 m²/g toabout 1,500 m²/g, about 250 m²/g to about 2,000 m²/g, about 250 m²/g toabout 2,500 m²/g, about 250 m²/g to about 3,000 m²/g, about 250 m²/g toabout 3,500 m²/g, about 500 m²/g to about 750 m²/g, about 500 m²/g toabout 1,000 m²/g, about 500 m²/g to about 1,500 m²/g, about 500 m²/g toabout 2,000 m²/g, about 500 m²/g to about 2,500 m²/g, about 500 m²/g toabout 3,000 m²/g, about 500 m²/g to about 3,500 m²/g, about 750 m²/g toabout 1,000 m²/g, about 750 m²/g to about 1,500 m²/g, about 750 m²/g toabout 2,000 m²/g, about 750 m²/g to about 2,500 m²/g, about 750 m²/g toabout 3,000 m²/g, about 750 m²/g to about 3,500 m²/g, about 1,000 m²/gto about 1,500 m²/g, about 1,000 m²/g to about 2,000 m²/g, about 1,000m²/g to about 2,500 m²/g, about 1,000 m²/g to about 3,000 m²/g, about1,000 m²/g to about 3,500 m²/g, about 1,500 m²/g to about 2,000 m²/g,about 1,500 m²/g to about 2,500 m²/g, about 1,500 m²/g to about 3,000m²/g, about 1,500 m²/g to about 3,500 m²/g, about 2,000 m²/g to about2,500 m²/g, about 2,000 m²/g to about 3,000 m²/g, about 2,000 m²/g toabout 3,500 m²/g, about 2,500 m²/g to about 3,000 m²/g, about 2,500 m²/gto about 3,500 m²/g, or about 3,000 m²/g to about 3,500 m²/g.

In some embodiments, active material has a conductivity of at leastabout 750 siemens/meter (S/m). In some embodiments, active material hasa conductivity of at most about 3,000 S/m. In some embodiments, activematerial has a conductivity of about 750 S/m to about 3,000 S/m. In someembodiments, active material has a conductivity of about 750 S/m toabout 1,000 S/m, about 750 S/m to about 1,500 S/m, about 750 S/m toabout 2,000 S/m, about 750 S/m to about 2,500 S/m, about 750 S/m toabout 3,000 S/m, about 1,000 S/m to about 1,500 S/m, about 1,000 S/m toabout 2,000 S/m, about 1,000 S/m to about 2,500 S/m, about 1,000 S/m toabout 3,000 S/m, about 1,500 S/m to about 2,000 S/m, about 1,500 S/m toabout 2,500 S/m, about 1,500 S/m to about 3,000 S/m, about 2,000 S/m toabout 2,500 S/m, about 2,000 S/m to about 3,000 S/m, or about 2,500 S/mto about 3,000 S/m.

In some embodiments, the two or more electrodes are arranged in anarray. In some embodiments, each electrode in the array is separatedfrom a subsequent electrode by a gap.

In some embodiments, the array is a planar array. In some embodiments,the number of electrodes is at least about 2.

In some embodiments, the width of the gap at least about 10 μm. In someembodiments, the width of the gap at most about 2,000 μm. In someembodiments, the width of the gap about from 10 μm to about 2,000 μm. Insome embodiments, the width of the gap about 10 μm to about 25 μm, about10 μm to about 50 μm, about 10 μm to about 100 μm, about 10 μm to about500 μm, about 10 μm to about 1,000 μm, about 10 μm to about 1,500 μm,about 10 μm to about 2,000 μm, about 25 μm to about 50 μm, about 25 μmto about 100 μm, about 25 μm to about 500 μm, about 25 μm to about 1,000μm, about 25 μm to about 1,500 μm, about 25 μm to about 2,000 μm, about50 μm to about 100 μm, about 50 μm to about 500 μm, about 50 μm to about1,000 μm, about 50 μm to about 1,500 μm, about 50 μm to about 2,000 μm,about 100 μm to about 500 μm, about 100 μm to about 1,000 μm, about 100μm to about 1,500 μm, about 100 μm to about 2,000 μm, about 500 μm toabout 1,000 μm, about 500 μm to about 1,500 μm, about 500 μm to about2,000 μm, about 1,000 μm to about 1,500 μm, about 1,000 μm to about2,000 μm, or about 1,500 μm to about 2,000 μm.

In some embodiments, the supercapacitor device further comprises anelectrolyte. In some embodiments, the electrolyte is a liquid, a solid,a gel, or any combination thereof. In some embodiments, the electrolytecomprises a polymer, silica, 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, phosphoric acid, tetraethyl ammoniumtetrafluoroborate (TEABF₄), acetonitrile,1-ethyl-3-methylimidazoliumtetrafluoroborate, ethanolammonium nitrate, adicarboxylate, a prostaglandin, adenosine monophosphate, guanosinemonophosphate, a p-aminohippurate, polysiloxane, polyphosphazene,potassium hydroxide, polyvinyl alcohol or any combination thereof. Insome embodiments, the silica is fumed silica. In some embodiments, thesilica is fumed silica and/or is in the form of a nano-powder.

In some embodiments, the electrolyte is aqueous and wherein the numberof electrodes is about 5. In this embodiment, the produced voltagepotential across the array of electrodes is at least about 2.5 volts(V). In some embodiments, produced voltage potential across the array ofelectrodes is at most about 10 V. In some embodiments, produced voltagepotential across the array of electrodes is about 2.5 V to about 10 V.In some embodiments, produced voltage potential across the array ofelectrodes is about 2.5 V to about 3 V, about 2.5 V to about 4 V, about2.5 V to about 5 V, about 2.5 V to about 6 V, about 2.5 V to about 8 V,about 2.5 V to about 10 V, about 3 V to about 4 V, about 3 V to about 5V, about 3 V to about 6 V, about 3 V to about 8 V, about 3 V to about 10V, about 4 V to about 5 V, about 4 V to about 6 V, about 4 V to about 8V, about 4 V to about 10 V, about 5 V to about 6 V, about 5 V to about 8V, about 5 V to about 10 V, about 6 V to about 8 V, about 6 V to about10 V, or about 8 V to about 10 V.

In some embodiments, the electrolyte comprises tetraethyl ammoniumtetrafluoroborate (TEABF₄) in acetonitrile and wherein the number ofelectrodes is about 5. In this embodiment, the produced voltagepotential across the array of electrodes is at least about 6 V. In someembodiments, produced voltage potential across the array of electrodesis at most about 24 V. In some embodiments, produced voltage potentialacross the array of electrodes is about 6 V to about 24 V. In someembodiments, produced voltage potential across the array of electrodesis about 6 V to about 8 V, about 6 V to about 10 V, about 6 V to about12 V, about 6 V to about 14 V, about 6 V to about 16 V, about 6 V toabout 18 V, about 6 V to about 20 V, about 6 V to about 22 V, about 6 Vto about 24 V, about 8 V to about 10 V, about 8 V to about 12 V, about 8V to about 14 V, about 8 V to about 16 V, about 8 V to about 18 V, about8 V to about 20 V, about 8 V to about 22 V, about 8 V to about 24 V,about 10 V to about 12 V, about 10 V to about 14 V, about 10 V to about16 V, about 10 V to about 18 V, about 10 V to about 20 V, about 10 V toabout 22 V, about 10 V to about 24 V, about 12 V to about 14 V, about 12V to about 16 V, about 12 V to about 18 V, about 12 V to about 20 V,about 12 V to about 22 V, about 12 V to about 24 V, about 14 V to about16 V, about 14 V to about 18 V, about 14 V to about 20 V, about 14 V toabout 22 V, about 14 V to about 24 V, about 16 V to about 18 V, about 16V to about 20 V, about 16 V to about 22 V, about 16 V to about 24 V,about 18 V to about 20 V, about 18 V to about 22 V, about 18 V to about24 V, about 20 V to about 22 V, about 20 V to about 24 V, or about 22 Vto about 24 V.

In some embodiments, the electrolyte is aqueous and wherein the numberof electrodes is about 180. In this embodiment, the produced voltagepotential across the array of electrodes is at least about 100 V. Insome embodiments, produced voltage potential across the array ofelectrodes is at most about 360 V. In some embodiments, produced voltagepotential across the array of electrodes is about 100 V to about 360 V.In some embodiments, produced voltage potential across the array ofelectrodes is about 100 V to about 150 V, about 100 V to about 200 V,about 100 V to about 250 V, about 100 V to about 300 V, about 100 V toabout 360 V, about 150 V to about 200 V, about 150 V to about 250 V,about 150 V to about 300 V, about 150 V to about 360 V, about 200 V toabout 250 V, about 200 V to about 300 V, about 200 V to about 360 V,about 250 V to about 300 V, about 250 V to about 360 V, or about 300 Vto about 360 V.

In some embodiments, the electrolyte comprises tetraethyl ammoniumtetrafluoroborate (TEABF₄) in acetonitrile and wherein the number ofelectrodes is about 72. In this embodiment, the produced voltagepotential across the array of electrodes is at least about 100 V. Insome embodiments, produced voltage potential across the array ofelectrodes is at most about 360 V. In some embodiments, produced voltagepotential across the array of electrodes is about 100 V to about 360 V.In some embodiments, produced voltage potential across the array ofelectrodes is about 100 V to about 150 V, about 100 V to about 200 V,about 100 V to about 250 V, about 100 V to about 300 V, about 100 V toabout 360 V, about 150 V to about 200 V, about 150 V to about 250 V,about 150 V to about 300 V, about 150 V to about 360 V, about 200 V toabout 250 V, about 200 V to about 300 V, about 200 V to about 360 V,about 250 V to about 300 V, about 250 V to about 360 V, or about 300 Vto about 360 V.

In some embodiments, the array of electrodes is a stacked array ofelectrodes. In some embodiments, the stacked array of electrodescomprises a plurality of electrodes.

In some embodiments, an electrode is a single-sided electrode, wherein afirst surface of the current collector contains an active material. Insome embodiments, an electrode is a double-sided electrode, wherein afirst and an, opposing, second surface of the current collector containan active material.

In some embodiments, the supercapacitor comprises an active material ona second surface of the current collector. In some embodiments, aportion the first surface of the current collector is not covered by anactive material. In some embodiments, a portion of the second surface ofthe current collector is not covered by an active material.

In some embodiments, a distal electrode in the stacked array comprises asingle-sided electrode. In some embodiments, the first surface of adistal electrode's current collector faces inwards. In some embodiments,a double-sided electrode is placed between two single-sided electrodes.In some embodiments, the number of double-active-sided electrodes in thestacked array is at least about 1.

In some embodiments, a separator positioned between each pair ofadjacent electrodes. In some embodiments, the separator is comprised ofcotton, cellulose, nylon, polyesters, glass, polyethylene,polypropylene, polytetrafluoroethylene, polyvinyl chloride,polyvinylidene fluoride, plastic, ceramics, rubber, asbestos, wood orany combination thereof.

In some embodiments, the stacked array further comprises a support thatmay be positioned between the first faces of a pair of adjacentsingle-active-sided electrodes. In some embodiments, the support iscomprised of steel, stainless steel, aluminum, wood, glass, plastic,carbon fiber, fiberglass, metal or any combination thereof.

A second aspect provided herein is a method of fabricating asupercapacitor comprising: fabricating an array of electrodescomprising: covering a portion of the first surface of a currentcollector; applying an active material onto the first surface of thecurrent collector; and drying the active material on the currentcollector.

In some embodiments the second aspect further comprises covering aportion of the second surface of the current collector; applying anactive material onto the second surface of the current collector; anddrying the active material on the current collector.

In some embodiments, at least one or more of a tape and a mask, shieldsa portion of the substrate to thereby prevent application of an activematerial onto the shielded portion of the substrate.

In some embodiments, the current collector comprises a metal film or apolymeric film or any combination thereof. In some embodiments, themetal film comprises silver, copper, gold, aluminum, calcium, tungsten,zinc, brass, bronze, nickel, lithium, iron, platinum, tin, carbon steel,lead, titanium, stainless steel, mercury, chromium, gallium arsenide orany combination thereof. In some embodiments, the polymeric filmcomprises polyfluorene, polyphenylene, polypyrene, polyazulene,polynaphthalene, polyacetylene, poly p-phenylene vinylene, polypyrrole,polycarbazole, polyindole, polyazepinem, polyaniline, polythiophene,poly 3,4-ethylenedioxythiophene, poly p-phenylene sulfide,polyacetylene, poly p-phenylene vinylene or any combination thereof.

In some embodiments, thickness of the current collector is at leastabout 50 nm. In some embodiments, thickness of the current collector isat most about 200 nm. In some embodiments, thickness of the currentcollector is about 50 nm to about 200 nm. In some embodiments, thicknessof the current collector is about 50 nm to about 75 nm, about 50 nm toabout 100 nm, about 50 nm to about 125 nm, about 50 nm to about 150 nm,about 50 nm to about 175 nm, about 50 nm to about 200 nm, about 75 nm toabout 100 nm, about 75 nm to about 125 nm, about 75 nm to about 150 nm,about 75 nm to about 175 nm, about 75 nm to about 200 nm, about 100 nmto about 125 nm, about 100 nm to about 150 nm, about 100 nm to about 175nm, about 100 nm to about 200 nm, about 125 nm to about 150 nm, about125 nm to about 175 nm, about 125 nm to about 200 nm, about 150 nm toabout 175 nm, about 150 nm to about 200 nm, or about 175 nm to about 200nm.

Some embodiments further comprise a step of adhering the currentcollector to a substrate. In some embodiments, the substrate compriseswood, glass, plastic, carbon fiber, fiberglass, metal or any combinationthereof.

In some embodiments, the current collector is partially covered by atape or a mask. In some embodiments, the tape comprises Kapton tapedouble-active-sided electrode tape, duct tape, electrical tape, filamenttape, gaffer tape, gorilla tape, masking tape, Scotch tape, surgicaltape, Teflon tape or any combination thereof.

In some embodiments, the active material is in the form of a slurry. Insome embodiments, the slurry is applied to the substrate by a doctorblade. In some embodiments, the processes of applying an active materialonto the first surface of the current collector and applying an activematerial onto the second surface of the current collector are performedsimultaneously.

In some embodiments, the drying of the active material on the currentcollector occurs at a temperature of at least about 40° C. In someembodiments, the drying of the active material on the current collectoroccurs at a temperature of at most about 160° C. In some embodiments,the drying of the active material on the current collector occurs at atemperature of about 40° C. to about 160° C. In some embodiments, thedrying of the active material on the current collector occurs at atemperature of about 40° C. to about 60° C., about 40° C. to about 80°C., about 40° C. to about 100° C., about 40° C. to about 120° C., about40° C. to about 140° C., about 40° C. to about 160° C., about 60° C. toabout 80° C., about 60° C. to about 100° C., about 60° C. to about 120°C., about 60° C. to about 140° C., about 60° C. to about 160° C., about80° C. to about 100° C., about 80° C. to about 120° C., about 80° C. toabout 140° C., about 80° C. to about 160° C., about 100° C. to about120° C., about 100° C. to about 140° C., about 100° C. to about 160° C.,about 120° C. to about 140° C., about 120° C. to about 160° C., or about140° C. to about 160° C.

In some embodiments, the drying of the active material on the currentcollector occurs over a period of time of at least about 6 hours. Insome embodiments, the drying of the active material on the currentcollector occurs over a period of time of at most about 24 hours. Insome embodiments, the drying of the active material on the currentcollector occurs over a period of time of about 6 hours to about 24hours. In some embodiments, the drying of the active material on thecurrent collector occurs over a period of time of about 6 hours to about8 hours, about 6 hours to about 10 hours, about 6 hours to about 12hours, about 6 hours to about 16 hours, about 6 hours to about 20 hours,about 6 hours to about 24 hours, about 8 hours to about 10 hours, about8 hours to about 12 hours, about 8 hours to about 16 hours, about 8hours to about 20 hours, about 8 hours to about 24 hours, about 10 hoursto about 12 hours, about 10 hours to about 16 hours, about 10 hours toabout 20 hours, about 10 hours to about 24 hours, about 12 hours toabout 16 hours, about 12 hours to about 20 hours, about 12 hours toabout 24 hours, about 16 hours to about 20 hours, about 16 hours toabout 24 hours, or about 20 hours to about 24 hours.

In some embodiments the second aspect further comprises a step offorming an array of two or more electrodes, wherein each electrode isseparated from a subsequent electrode by a gap. In some embodiments, thearray is planar array, and wherein the planar array comprises asingle-active-sided electrode, a double-active-sided electrode or anycombination thereof. In some embodiments, the planar array is fabricatedby etching or cutting the active material and the current collector. Insome embodiments, the process of etching or cutting the active materialon the current collector and the current collector is performed by alaser, a knife, a blade, scissors or any combination thereof.

In some embodiments, the width of the gap at least about 10 μm. In someembodiments, the width of the gap at most about 2,000 μm. In someembodiments, the width of the gap about from 10 μm to about 2,000 μm. Insome embodiments, the width of the gap about 10 μm to about 25 μm, about10 μm to about 50 μm, about 10 μm to about 100 μm, about 10 μm to about500 μm, about 10 μm to about 1,000 μm, about 10 μm to about 1,500 μm,about 10 μm to about 2,000 μm, about 25 μm to about 50 μm, about 25 μmto about 100 μm, about 25 μm to about 500 μm, about 25 μm to about 1,000μm, about 25 μm to about 1,500 μm, about 25 μm to about 2,000 μm, about50 μm to about 100 μm, about 50 μm to about 500 μm, about 50 μm to about1,000 μm, about 50 μm to about 1,500 μm, about 50 μm to about 2,000 μm,about 100 μm to about 500 μm, about 100 μm to about 1,000 μm, about 100μm to about 1,500 μm, about 100 μm to about 2,000 μm, about 500 μm toabout 1,000 μm, about 500 μm to about 1,500 μm, about 500 μm to about2,000 μm, about 1,000 μm to about 1,500 μm, about 1,000 μm to about2,000 μm, or about 1,500 μm to about 2,000 μm.

In some embodiments the second aspect further comprises dispersing anelectrolyte onto an electrode. In some embodiments, the electrolyte is aliquid, a solid, a gel, or any combination thereof. In some embodiments,the electrolyte comprises a polymer, silica, 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, phosphoric acid, tetraethyl ammoniumtetrafluoroborate, acetonitrile,1-ethyl-3-methylimidazoliumtetrafluoroborate, ethanolammonium nitrate, adicarboxylate, a prostaglandin, adenosine monophosphate, guanosinemonophosphate, a p-aminohippurate, polysiloxane, polyphosphazene or anycombination thereof. In some embodiments, the silica is fumed. In someembodiments, the silica is fumed and/or is in the form of a nano-powder.

In some embodiments, the array is a stacked array. In some embodiments,the stacked array comprises a plurality of electrodes. In someembodiments, the distal electrodes in the stacked array have an activematerial only on the first surface of the current collector, and whereinthe first surface of the current collector faces inwards. In someembodiments, the stacked array comprises one or more electrodes whichhave an active material on both a first and a second surface of itscurrent collector, wherein the one or more electrodes which have anactive material on both a first and a second surface of its currentcollector may be positioned between the single-active-sided electrodes.

In some embodiments, a separator positioned between each pair ofconsecutive electrodes. In some embodiments, the separator is comprisedof cotton, cellulose, nylon, polyesters, glass, polyethylene,polypropylene, polytetrafluoroethylene, polyvinyl chloride,polyvinylidene fluoride, plastic, ceramics, rubber, asbestos, wood orany combination thereof.

In some embodiments, the stacked array further comprises a supportpositioned between an electrode and a subsequent electrode. In someembodiments, the support is comprised of steel, stainless steel,aluminum, wood, glass, plastic, carbon fiber, fiberglass, metal or anycombination thereof.

In some embodiments the second aspect further comprises: dispersing anelectrolyte on the stacked array; encasing the stacked array in asheath; inserting the encased stacked array into a housing; or anycombination thereof.

In some embodiments, the electrolyte is a liquid, a solid, a gel, or anycombination thereof. In some embodiments, the electrolyte comprises apolymer, silica, 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, phosphoric acid, tetraethyl ammoniumtetrafluoroborate, acetonitrile,1-ethyl-3-methylimidazoliumtetrafluoroborate, ethanolammonium nitrate, adicarboxylate, a prostaglandin, adenosine monophosphate, guanosinemonophosphate, a p-aminohippurate, polysiloxane, polyphosphazene or anycombination thereof. In some embodiments, the silica is fumed. In someembodiments, the silica is fumed and/or is in the form of a nano-powder.

In some embodiments, the housing comprises: two or more terminals; agasket; a container; or any combination thereof.

Other goals and advantages of the disclosure will be further appreciatedand understood when considered in conjunction with the followingdescription and accompanying drawings. While the following descriptionmay contain specific details describing particular embodiments of thedisclosure, this should not be construed as limitations to the scope ofthe disclosure but rather as an exemplification of preferableembodiments. For each aspect of the disclosure, many variations arepossible as suggested herein that are known to those of ordinary skillin the art. A variety of changes and modifications may be made withinthe scope of the disclosure without departing from the spirit thereof

Supercapacitors

Supercapacitors (also known as “ultracapacitors”), are high powerdensity energy storage devices, with a much higher capacitance thannormal capacitors, that have recently attracted considerable attention,and have been increasingly employed as high power density energy storageresources in portable electronic devices, medical devices and hybridelectric vehicles due to recent technological advancements.

Supercapacitors are attractive means of energy storage because they mayexhibit ultrafast charge and discharge times on the order of secondscompared with hours for conventional batteries. Additionally,supercapacitors may play an important role in the progress of hybrid andelectric vehicles, consumer electronics, and military and spaceapplications. Current supercapacitors, however, often require multiplecells packaged either in series, in parallel, or in combinations thereofin order to meet energy and power requirements of portable electronics.

In some embodiments, supercapacitors or electrochemical capacitors arecomprised of two or more electrodes separated by an ion-permeablemembrane (separator), and an electrolyte ionically connecting theelectrodes, whereas ions in the electrolyte form electric double layersof opposite polarity to the electrode's polarity when the electrodes arepolarized by an applied voltage.

Supercapacitors may be classified according to their charge storagemechanism as either electric double-layer capacitors (EDLCs) or redoxsupercapacitors. In some embodiments, a supercapacitor may be adouble-layer supercapacitor, pseudocapacitor or a hybrid supercapacitor.

High-voltage devices (“devices”) of the disclosure may compriseinterconnected cells, whereas each cell comprises two or more electrodesseparated by a gap distance. In some embodiments, the cells may beelectrochemical cells (e.g., individual supercapacitor cells). Two ormore cells may be interconnected, for example, to achieve a high voltage(and/or for other purposes).

In some embodiments, a supercapacitor may be formed with a stacked (orsandwich) structure. In some embodiments, a stacked structure iscomprised of two or more thin-film electrodes assembled face-to-face,which are separated by a separator that prevents electrical shorting.

In some embodiments, a supercapacitor may be formed with a planarstructure. In some embodiments, a planar supercapacitor is comprised ofelectrodes designed in a planar configuration. Planar supercapacitorsmay have several advantages over the stacked design. First, asupercapacitor with electrodes in the same plane may be compatible withon-chip integration. Second, the traveling distance of the ions in theelectrolyte, a major performance factor in supercapacitors, may be wellcontrolled and shortened while eliminating the necessity of theseparator required in stacked supercapacitors. Third, the structure maybe extended to three dimensions, to increase its density whilemaintaining the mean ionic diffusion path. This architecture thus mayhave the potential to achieve high power densities and at high energydensities. Additionally, in some embodiments, in-plane devices mayexhibit a simple structure of several cells which may be assembled inone step. In some embodiments, fabricated planar arrays of cells may bepackaged using one package.

Electrode

In some embodiments, an electrode in an electrochemical cell comprises acurrent collector and an active material, and is referred to as eitheran anode, whereas electrons leave the active material within a cell andoxidation occurs, or as a cathode, whereas the electrons enter theactive material within a cell and reduction occurs. Each electrode maybecome either the anode or the cathode depending on the direction ofcurrent through the cell.

In some embodiments, a single-sided electrode is comprised of a currentcollector and an active material whereas the active material is disposedon only one face of the current collector.

In some embodiments, a double-sided electrode is comprised of a currentcollector and an active material whereas the active material is disposedon both opposing faces of the current collector.

In some embodiments, a double-sided electrode disposed between, andseparated by a gap from, two single-sided electrodes, whose activematerial faces inwards, forms a two-celled supercapacitor.

Materials commonly employed in supercapacitor electrodes includetransition-metal oxides, conducting polymers, and high-surface carbons.

Current Collector

In some embodiments, a current collector connects the electrodes to acapacitor's terminals. In some embodiments, a current collector is afoil or a coating that is conductive, chemically stable, and corrosionresistant. In some embodiments, a current collector may be comprised ofsilver, copper, gold, aluminum, calcium, tungsten, zinc, tungsten,brass, bronze, nickel, lithium, iron, platinum, tin, carbon steel, lead,titanium, stainless steel, mercury, chromium, gallium arsenide,polyimide, polyfluorene, polyphenylene, polypyrene, polyazulene,polynaphthalene, polyacetylene, poly p-phenylene vinylene, polypyrrole,polycarbazole, polyindole, polyazepinem, polyaniline, polythiophene,poly 3,4-ethylenedioxythiophene, poly p-phenylene sulfide,polyacetylene, poly p-phenylene vinylene or any combination thereof.

In some embodiments, the thickness of the current collector is about 50nanometers to about 200 nanometers.

Active Material

In some embodiments, an active material is the component within anelectrode that participates in the electrochemical charge and dischargereaction, and may comprise carbonaceous and/or other suitable materials.In some embodiments, the active material comprises carbon, activatedcarbon, carbon cloth, carbon fiber, amorphous carbon, glassy carbon,carbon nanofoam, carbon aerogel, graphene, polyaniline, polythiophene,interconnected corrugated carbon-based network (ICCN) or any combinationthereof.

In some embodiments, ICCN comprises a plurality of expanded andinterconnected carbon layers. In some embodiments, each carbon layer isa two-dimensional, one atom thick sheet of carbon. In some embodiments,one or more of the expanded and interconnected carbon layers comprise aone atom thick corrugated carbon sheet. An ICCN may exhibit a highsurface area and a high electrical conductivity.

In certain embodiments, the term “expanded,” refers to a plurality ofcarbon layers that are expanded apart from one another, whereas aportion of adjacent carbon layers are separated by at least about 2nanometers (nm). In some embodiments, at least a portion of adjacentcarbon layers are separated by a gap of greater than or equal to about 1nm.

In some embodiments, a plurality of carbon layers has an electricalconductivity of at least about 750 siemens/meter (S/m). In someembodiments, a plurality of carbon layers has an electrical conductivityof at most about 3,000 S/m. In some embodiments, a plurality of carbonlayers has an electrical conductivity of about 750 S/m to about 3,000S/m.

In some embodiments, a plurality of carbon layers has a surface densityof at least about 250 meters squared per gram (m²/g). In someembodiments, a plurality of carbon layers has a surface density of atmost about 3,500 m²/g. In some embodiments, a plurality of carbon layershas a surface density of from about 250 m²/g to about 3,500 m²/g.

Electrolyte

In some embodiments, an electrolyte is a substance that produces anelectrically conducting solution when dissolved in a polar solvent. Insome embodiments, if an electric potential is applied to such asolution, the cations of the solution are drawn to the electrode thathas an abundance of electrons, while the anions are drawn to theelectrode that has a deficiency of electrons. The movement of anions andcations in opposite directions within the solution draws a current.

In some embodiments, electrolytes may be comprised of an aqueouselectrolyte, an organic electrolyte, an ionic liquid-based electrolyte,or any combination thereof. In some embodiments, an electrolyte may beliquid, solid or a gel (ionogel). In some embodiments, an ionic liquidmay be hybridized with another solid component such as for example,polymer, silica or fumed silica to form a gel-like electrolyte. In someembodiments, an aqueous electrolyte may be hybridized with, for example,a polymer, to form a gel-like electrolyte (also “hydrogel” or“hydrogel-polymer”). In some embodiments, an organic electrolyte may behybridized with, for example, a polymer, to form a gel-like electrolyte.In some embodiments, the electrolyte is comprised of aqueous potassiumhydroxide, a hydrogel comprising poly(vinyl alcohol) (PVA)-H₂SO₄ orPVA-H₃PO₄, an aqueous solution of phosphoric acid (H₃PO₄), tetraethylammonium tetrafluoroborate (TEABF₄) dissolved in acetonitrile,1-ethyl-3-methylimidazoliumtetrafluoroborate (EMIMBF₄), an ionogelcomprising fumed silica (e.g., fumed silica nano-powder) mixed with anionic liquid (e.g., 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide (BMIMNTf₂)), or any combinationthereof.

Separator

In some embodiments, a separator is a permeable membrane placed betweena battery's or supercapacitor's anode and cathode electrodes. In someembodiments, a separator maintains a gap distance between two adjacentelectrodes to prevent electrical short circuits while also allowing thetransport of ionic charge carriers that are needed to close the circuitduring the passage of current in an electrochemical cell. In someembodiments, a separator absorbs an electrolyte to increase conductivitybetween the electrodes.

A separator may be a critical component in a liquid electrolyte energystorage device because its structure and properties considerably affectan energy storage device's performance characteristics such as itsenergy and power density, cycle life, and safety. In some embodiments, aseparator is comprised of a polymeric membrane that forms a chemicallyand electrochemically stable microporous layer, with regard to theelectrolyte and electrode materials, and exhibits sufficient mechanicalstrength to withstand battery construction and use. In some embodiments,a separator comprises a single layer/sheet or multiple layers/sheets ofmaterial. In some embodiments, a separator comprises a nonwoven fibercomprising a web or mat of directionally or randomly oriented fibers,supported liquid membranes comprising solid and liquid materials withina microporous structure, a polymer, or any combination thereof.

In some embodiments, a separator is placed between two electrode'sactive material surfaces.

In some embodiments, polymer electrolytes form complexes with alkalimetal salts, which produce ionic conductors that serve as solidelectrolytes. In some embodiments, a solid ion conductor may serve asboth a separator and the electrolyte.

In some embodiments, separators are comprised of cotton, cellulose,nylon, polyesters, glass, polyethylene, polypropylene,polytetrafluoroethylene, polyvinyl chloride, polyvinylidene fluoride,plastic, ceramics, rubber, asbestos, wood or any combination thereof.

Support

In some embodiments, a support is a conductive material placed betweensupercapacitor electrodes that increases the rigidity of thesupercapacitor device. In some embodiments, a support is placed betweentwo electrodes in contact with each of their current collector'ssurfaces without an active material coating.

In some embodiments, the support is composed of any conducting materialcomprising scandium, titanium, vanadium, chromium, manganese, iron,cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum,technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium,tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury orany combination thereof.

Seal

In some embodiments, a seal is used to prevent an electrolyte fromleaking out a supercapacitor cell and potentially cause short circuit.Additionally, a seal may increase the rigidity and durability of astacked supercapacitor device by constraining one or more of thesupercapacitor's cells. In some embodiments, the seal may be formed of achemical resistant and waterproof material that does not degrade uponcontact with the electrolyte. In some embodiments, the seal is comprisedof glue, epoxy, resin, tubing, plastic, fiberglass, glass or anycombination thereof.

Housing

In some embodiments, the components of a supercapacitor device arestored within a housing to increase durability and prevent electrolyteleakage. In some embodiments, the housing comprises a preformedcomponent, a component formed around the supercapacitor components orany combination thereof. In some embodiments, the housing acts as thenegative or positive terminal. In some embodiments, the housing of asupercapacitor device is comprised of metal, plastic, wood, carbonfiber, fiberglass, glass or any combination thereof.

In some embodiments, the housing of a supercapacitor device additionallycomprises a tab, a terminal, a gasket or any combination thereof. Insome embodiments, a tab transmits electricity from the sealed electrodesto the positive terminal or the negative terminal. In some embodiments,the positive terminal or the negative terminal connect the sealedelectrodes to an electronic device which consumes the energy storedtherein. In some embodiments, the tabs and terminals may be composed ofany conducting material comprising scandium, titanium, vanadium,chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium,zirconium, niobium, molybdenum, technetium, ruthenium, rhodium,palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium,osmium, iridium, platinum, gold, mercury or any combination thereof. Insome embodiments, the tabs and terminals may be composed of a polymercontaining traces of a conducting material. In some embodiments, thegasket is comprised of water resistant material including plastics,metals, resins or any combination thereof.

REFERENCES TO THE FIGURES

Exemplary illustrations of high-voltage supercapacitor devices are shownin FIGS. 1A-1D. An exemplary single-cell linear supercapacitor device100, per FIG. 1A, comprises two wires 103, and an array of twoelectrodes 110, whereas each electrode 110 comprises a current collector101, and an active material 102. A single supercapacitor cell is definedby a pair of electrodes 110 separated by a dielectric gap.

FIG. 1B displays an exemplary 2-cell linear supercapacitor device 150comprising a linear array of one isobilateral electrode 120 and twoanisobilateral electrodes 110, whereas the isobilateral electrode 120contains one portion of its current collector that is covered by theactive material 102, and wherein the anisobilateral electrode 110contains two distal portions of its current collector that are coveredby the active material 102. In some embodiments, the anisobilateralelectrode 110 is arranged such that its side that is covered by theactive material is aligned distally within the array. In someembodiments, the 2-cell linear supercapacitor device 150 is capable ofproducing twice the voltage as a single-cell supercapacitor device 100.FIG. 1C displays an exemplary 5-cell linear supercapacitor device 160comprising a linear array of four isobilateral electrodes 120 and twoanisobilateral electrodes 110. In some embodiments, the 5-cell linearsupercapacitor device 160 is capable of producing five times the voltageas a single-cell supercapacitor device 100.

Per FIGS. 1B and 1C, the distal electrodes in the array compriseanisobilateral electrodes 110, whereas the 1 or 4 proximal electrodescomprise isobilateral electrodes 120, respectively. Additionally, eachpair of consecutive electrodes is separated by a set gap distance whichacts as an insulating layer (or dielectric separator).

As seen, in FIGS. 1B-1D, a portion of the current collectors 101 of thedistal anisobilateral electrodes 110 is not covered by the activematerial 102, to allow for the adhesion of a wire 103, capable ofelectrical connection with other devices or device components such as aterminal. Additionally, per FIGS. 1B-1D, a portion of the currentcollectors 101 of the proximal isobilateral electrodes 120 is notcovered by the active material 102, to form a boundary between cells.

In addition to the single-cell supercapacitor device 100 and the linearsupercapacitor devices 150 160 displayed in FIGS. 1A-C, an exemplaryplanar supercapacitor device 200, as shown in FIG. 2, may comprise a twodimensional array of a series of 180 electrodes, wherein the first andlast electrodes in the series of electrodes are anisobilateralelectrodes 210, wherein the distal electrodes, that are not the first orlast electrode in the series of electrodes, in each row of the twodimensional array of electrodes comprise a C-shaped isobilateralelectrode 230, and wherein the proximal electrodes in each row of thetwo dimensional array of electrodes comprise isobilateral electrodes220. In some embodiments, the 180-cell linear supercapacitor device 200is capable of producing 180 times the voltage as a single-cellsupercapacitor device.

In principle, there may be no limit to the number of the cells that maybe arranged in two dimensional planar series. Only the voltage requiredfor the operation of the unit may define the total number of electrodesneeded for the unit.

FIGS. 3A and 3B show exemplary illustrations of a single-sided electrode300 and a double-sided electrode 310, respectively, wherein asingle-sided electrode 300 is comprised of a current collector 301 withan active material 302 deposited on a first surface of the currentcollector 301, and wherein a double-sided electrode 310 is comprised ofa current collector 301 with an active material 302 deposited on both afirst and on the opposing, second surface, of the current collector 301.

In some embodiments, the anisobilateral electrodes 110 210, isobilateralelectrodes 120 220, or the C-shaped isobilateral electrodes 230, shownin the exemplary supercapacitor devices 100 200 in FIGS. 1-2 maycomprise a single-sided electrode 300 or a double-sided electrode 310 orany combination thereof.

In some embodiments, stacked arrays of cells may be assembled into asingle package. FIGS. 4A-B show exemplary front and top cross-sectionalillustrations of a first preferred mode of a stacked supercapacitordevice assembly 400 comprising an electrode stack 450, a housing 403, atab 404, a positive terminal 405, a negative terminal 406, and a gasket407, wherein the electrode stack 450 comprises two single-sidedelectrodes 410, one or more double-sided electrodes 420, one or moreseparators 401, and a seal 402. In some embodiments, the distalelectrodes in the electrode stack 450 are single-sided electrodes 410,wherein the surface of each single-sided electrode 410 without theactive material faces outwards.

In some embodiments, a separator 401 is inserted between each electrodeto provide an insulating layer and prevent a short circuit. In someembodiments, an electrolyte is deposited onto each single-sidedelectrode 410 and double-sided electrode 420, wherein the seal 402prevents electrolyte leakage and potential short circuit. In someembodiments, the electrode stack 450 is protected by a housing 403. Insome embodiments, the housing 403 contains two tabs 404 which transmitelectricity from the electrode stack 450 to the positive terminal 405 orthe negative terminal 406, and/or a gasket 407 which seals the contentsof the housing 403.

Although the exemplary stacked supercapacitor device assembly 400 shownin FIGS. 4A-B comprises an electrode stack 450 with two single-sidedelectrodes 410 and one double-sided electrode 420, alternativesupercapacitor device assemblies may include any number of double-sidedelectrodes 420.

FIG. 5A shows an exemplary cross-sectional illustration of a secondpreferred mode of a supercapacitor device assembly 500, wherein theelectrode stack 550 comprises one or more single-sided electrodes 510.As shown, the first surface of each distal single-sided electrode 510(without the active material) in the electrode stack 550 faces outwards.In some embodiments, a separator 501 is inserted between eachsingle-sided electrode's 510 first surface, and a support 502 isinserted between each single-sided electrode's 510 second surface.

In some embodiments, per FIG. 5B, the support 502 may be adhered betweentwo current collector's first surfaces prior to the disposing of theactive material on each current collector to form a supporteddouble-sided electrode 560.

FIGS. 6A-C show illustrations of an exemplary packaged single cellsupercapacitor 600 comprising a housing 603, two single-sided electrodes610, a separator 620, a positive terminal 605 and a gasket 607. In someembodiments, the packaged single cell supercapacitor 600 additionallycomprises an electrolyte disposed on the single-sided electrodes 610.

In some embodiments, the exemplary packaged single cell supercapacitor600 is fabricated by inserting a first single-sided electrode 610,active material faced up, into the housing 603, placing a separator 620on the first single-sided electrode 610, placing a second single-sidedelectrode 610, active material faced down, atop the separator 620,inserting the positive terminal 605 and the gasket 607, crimping thehousing 603 to secure the contents within, or any combination thereof.

In some embodiments, the support is comprised of any rigid, conductingand chemical resistant material such as stainless steel, plastic, metal,glass or any combination thereof.

In some embodiments, a single-sided supercapacitor electrode isfabricated by partially covering a first surface of a current collector,applying an active material onto the first surface of the currentcollector and drying the active material on the current collector toform a single-sided electrode.

In some embodiments, a double-sided supercapacitor electrode isfabricated by partially covering the second surface of the single-sidedelectrode's current collector, applying an active material onto thesecond surface of the single-sided electrode's current collector anddrying the active material on the current collector to form adouble-sided electrode. In further embodiments, a double-sided electrodemay be fabricated by coating both the first and second surfaces of acurrent collector simultaneously and drying the active material on thecurrent collector.

Images of an exemplary method of applying the active material onto afirst or second surface of a current collector are shown in FIG. 7,whereas a doctor blade 702 is employed to apply a uniform thickness ofan active material slurry 701 onto the current collector, and whereas atape 703 is used to cover, and prevent the application of the activematerial slurry 701 onto a portion of the first and/or second surface ofthe current collector. In some embodiments, a doctor blade is a devicewhich uniformly spreads a liquid or slurry onto a surface. In otherembodiments, a rotogravure is employed to maintain a uniform activematerial thickness. In other embodiments, a mask is used to cover, andprevent the application of the active material slurry 701 onto portionsof the first and/or second surface of the current collector. Theresulting electrode is shown in FIG. 8.

In some embodiments, the current collector is adhered to a substrate704, to stabilize and flatten the current collector. In the exemplarymethod, per FIG. 7, a tape 703 is used to both cover portions of thefirst surface of the current collector, and to adhere the currentcollector to the substrate 704. In some embodiments, the tape 703comprises Kapton tape, polyimide, double-sided tape, duct tape,electrical tape, filament tape, gaffer tape, gorilla tape, masking tape,Scotch tape, surgical tape, Teflon tape or any combination thereof. Insome embodiments, the substrate 704 comprises glass, wood, foam, carbonfiber, fiberglass, plastic, metal or any combination thereof.

An exemplary image of the active material applied on the currentcollector 801, is shown in FIG. 8.

In some embodiments, the active material is dried after its applicationto the current collector. In some embodiments, the active material andthe current collector are dried in an oven. In some embodiments, theactive material and the current collector are dried at a temperature ofabout 40° C. to 160° C. In some embodiments, the active material and thecurrent collector are dried for a period of time of about 6 hours to 24hours. FIGS. 9A-B show exemplary images of the dried electrode 900 andthe stripped electrode 910, after the tape and excess active material onthe tape have been removed.

In some embodiments, a planar array of electrodes is formed by etchingor cutting the dried active material and the current collector. In someembodiments, the process of etching or cutting the active material onthe current collector and the current collector is performed by a laser,a knife, a blade, scissors or any combination thereof. In someembodiments, a gap is thereby created.

In some embodiments, the width of the gap at least about 10 μm. In someembodiments, the width of the gap at most about 2,000 μm. In someembodiments, the width of the gap about from 10 μm to about 2,000 μm. Insome embodiments, the width of the gap about 10 μm to about 25 μm, about10 μm to about 50 μm, about 10 μm to about 100 μm, about 10 μm to about500 μm, about 10 μm to about 1,000 μm, about 10 μm to about 1,500 μm,about 10 μm to about 2,000 μm, about 25 μm to about 50 μm, about 25 μmto about 100 μm, about 25 μm to about 500 μm, about 25 μm to about 1,000μm, about 25 μm to about 1,500 μm, about 25 μm to about 2,000 μm, about50 μm to about 100 μm, about 50 μm to about 500 μm, about 50 μm to about1,000 μm, about 50 μm to about 1,500 μm, about 50 μm to about 2,000 μm,about 100 μm to about 500 μm, about 100 μm to about 1,000 μm, about 100μm to about 1,500 μm, about 100 μm to about 2,000 μm, about 500 μm toabout 1,000 μm, about 500 μm to about 1,500 μm, about 500 μm to about2,000 μm, about 1,000 μm to about 1,500 μm, about 1,000 μm to about2,000 μm, or about 1,500 μm to about 2,000 μm. In some embodiments, thenumber of cells is at least 2.

FIG. 10 shows an exemplary image of a 180-cell supercapacitor device 900formed by laser cutting the current collector and active material into apatterned array of electrodes. In some embodiments, the 180-cellsupercapacitor device 1000 comprises a single-sided electrode, adouble-sided electrode or any combination thereof.

FIG. 11 shows an exemplary image of the 180-cell supercapacitor device1100 during electrochemical testing, whereas an electrolyte may bedisposed onto one or more of the cell's electrodes.

FIGS. 12A-E show exemplary cyclic voltammetry (CV) graphs at scan ratesof 500 mV/s, 100 mV/s, 50 mV/s, 30 mV/s, and 10 mV/s, respectively. Insome embodiments, cyclic voltammetry is an electrochemical techniquewhich measures the current that develops in an electrochemical cellunder applied voltages. In some embodiments of CV testing, the electrodepotential ramps linearly versus time in cyclical phases, whereas therate of voltage change over time during each of these phases is known asthe scan rate.

FIG. 13 shows an overlay of the exemplary CV graphs at different scanrates, while FIG. 14 shows the charge and discharge waveform CV graph ata constant current.

FIG. 15 shows the Warburg impedance as the only impedance element forthe functional high-voltage. In some embodiments, the Warburg diffusionelement is an equivalent electrical circuit component that models thediffusion process in dielectric spectroscopy. In some embodiments, anequivalent circuit refers to a theoretical circuit that retains all ofthe electrical characteristics of a given circuit.

In some embodiments, a supercapacitor may be comprised of at least about2 cells.

In some embodiments, an exemplary single cell supercapacitor deviceproduced by the method described herein, and with an aqueouselectrolyte, is capable of producing a potential of about 1 V.

In some embodiments, an exemplary 5-cell supercapacitor device producedby the method described herein, and with an aqueous electrolyte, iscapable of producing a potential of from about 2.5 V to about 10 V.

In some embodiments, an exemplary 72-cell supercapacitor device producedby the method described herein, and with an aqueous electrolyte, iscapable of producing a potential of from about 6 V to about 24 V.

In some embodiments, an exemplary 180-cell supercapacitor deviceproduced by the method described herein, and with an aqueouselectrolyte, is capable of producing a potential of from about 100 V toabout 360 V.

In some embodiments, an exemplary single cell supercapacitor deviceproduced by the method described herein, and with tetraethyl ammoniumtetrafluoroborate (TEABF₄) in acetonitrile electrolyte, is capable ofproducing a potential of from about 2.5 V to about 10 V.

In some embodiments, an exemplary 5-cell supercapacitor device producedby the method described herein, and with tetraethyl ammoniumtetrafluoroborate (TEABF₄) in acetonitrile electrolyte, is capable ofproducing a potential of from about 6 V to about 24 V.

In some embodiments, an exemplary 72-cell supercapacitor device producedby the method described herein, and with tetraethyl ammoniumtetrafluoroborate (TEABF₄) in acetonitrile electrolyte, is capable ofproducing a potential of from about 100 V to about 360 V.

In some embodiments, an exemplary 180-cell supercapacitor deviceproduced by the method described herein, and with tetraethyl ammoniumtetrafluoroborate (TEABF₄) in acetonitrile electrolyte, is capable ofproducing a potential of from about 100 V to about 360 V.

Aspects of the disclosure described herein may be used in combination.Additionally, the systems and methods of the disclosure may be adaptedto other active materials. For example, during fabrication of planararrays of cells (e.g., by masking, coating, drying and patterningelectrodes), two-step electrode coating (and other fabrication stepssuch as, for example, masking) may be used to fabricate adjacentelectrodes comprising different (or asymmetric) active materials. Suchembodiments may enable, for example, fabrication of batteries comprisinga plurality of interconnected battery cells, or other devices (e.g.,photovoltaics, thermoelectrics or fuel cells) comprising cells withdifferent (or asymmetric) electrodes.

Terms and Definitions

As used herein, and unless otherwise defined, the term “corrugated”refers to a structure with a series of parallel ridges and furrows.

As used herein, and unless otherwise defined, the term “specific surfacearea” or “surface density” refers to a property of solids defined as thetotal surface area of a material per unit of mass.

As used herein, and unless otherwise defined, the term “conductivity” or“specific conductance” refers to the degree to which a specifiedmaterial conducts electricity, calculated as the ratio of the currentdensity in the material to the electric field that causes the flow ofcurrent.

As used herein, and unless otherwise defined, the term “planar” refersto a two-dimensional element lying primarily on a single plane.

As used herein, and unless otherwise defined, the term “stacked array”refers to a column, row or sandwich of elements.

As used herein, and unless otherwise defined, the term “aqueous” means asolution of a solvent and/or a solute, wherein either the solvent orsolute are liquid in form.

As used herein, and unless otherwise defined, the term “gel” refers to asolid jelly-like material that may have properties ranging from soft andweak to hard and tough. Gels may be defined as a substantially dilutecross-linked system, which exhibits no flow when in the steady-state.

As used herein, and unless otherwise defined, the term “fumed silica” orpyrogenic silica refers to silica produced in a flame, which may consistof microscopic droplets of amorphous silica fused into branched,chainlike, three-dimensional secondary particles, which may thenagglomerate to form tertiary particles.

As used herein, and unless otherwise defined, the term “isobilateralelectrode” refers to an electrode with a geometrical symmetry about itsvertical midplane.

As used herein, and unless otherwise defined, the term “anisobilateralelectrode” refers to an electrode without a geometrical symmetry aboutits vertical midplane.

Unless otherwise defined, all technical terms used herein have the samemeaning as commonly understood by one of ordinary skill in the art towhich this disclosure belongs. As used in this specification and theappended claims, the singular forms “a,” “an,” and “the” include pluralreferences unless the context clearly dictates otherwise. Any referenceto “or” herein is intended to encompass “and/or” unless otherwisestated.

As used herein, and unless otherwise defined, the term “about” refers toa range of values plus or minus 10% of the specified value.

While preferable embodiments of the present disclosure have been shownand described herein, it will be obvious to those skilled in the artthat such embodiments are provided by way of example only. Numerousvariations, changes, and substitutions will now occur to those skilledin the art without departing from the disclosure. It should beunderstood that various alternatives to the embodiments of thedisclosure described herein may be employed in practicing thedisclosure. It is intended that the following claims define the scope ofthe disclosure and that methods and structures within the scope of theseclaims and their equivalents be covered thereby.

Non-Limiting Embodiments

Additional non-limiting embodiments of the devices herein are listedbelow.

The present disclosure relates to a simple technique for the directpreparation of high-voltage devices such as, for example, high-voltagesupercapacitors. The high-voltage devices may be prepared in a singlestep. The high-voltage devices may be prepared using one package. Thehigh-voltage devices may be prepared in a single step and using onepackage. One package may advantageously be used instead of a pluralityof packages (e.g., instead of hundreds in the traditional modules). Insome embodiments, the high-voltage devices (e.g., high-voltagesupercapacitors) herein may have a voltage in excess of about 180 V (andup to about 540 V). However, it is to be understood that even highervoltages are achievable depending on chemistry, total number ofelectrodes in series, and physical dimensions. Examples include directpreparation of high-voltage supercapacitors (e.g., in excess of about180 V (and up to about 540 V)) in a single step and using one package(instead of a plurality, such as, for example, instead of hundreds inthe traditional modules).

High-voltage devices (“devices”) of the disclosure may compriseinterconnected cells. In some embodiments, the electrodes may beelectrochemical electrodes (e.g., individual supercapacitor cells). Theelectrodes may be interconnected, for example, to achieve a high voltage(and/or for other purposes).

A device such as, for example, a supercapacitor (e.g., double-layersupercapacitor, pseudocapacitor or hybrid supercapacitor), may be of agiven type (e.g., with a given configuration or structure). For example,two main types of supercapacitors may differ by structure: a sandwichstructure in which two thin-film electrodes are put togetherface-to-face with polymer plastic separator, and another structure thatconsists of micro-electrodes designed in a planar configuration. Planarsupercapacitors may have several advantages over the stacked design.First, having both electrodes in the same plane is compatible withon-chip integration. Second, the traveling distance of the ions in theelectrolyte, a major performance factor in supercapacitors, may be wellcontrolled and shortened while eliminating the necessity of a separator(which is used in the sandwich-type supercapacitors to preventelectrical shorting). Third, the structure may potentially be extendedto three dimensions, which allows more materials loaded per unit areawhile leaving the mean ionic diffusion path unaffected. Thisarchitecture thus has the potential to achieve high power density andhigh energy density in a small footprint.

Provided in certain embodiments are planar electrodes. Because of thesimple structure of the in-plane device, several electrodes may be puttogether and assembled in one step, as will be explained later.Fabricated planar arrays of electrodes may be packaged using onepackage.

A planar supercapacitor consists of two carbon electrodes: one of themis used as the positive electrode and the other as the negativeelectrode. The electrodes are made by coating the active material onto ametallic sheet. The spacing in between, acts as a dielectric separator.A cross-sectional view of this device is shown in diagram where is apart of the metallic foil that is left uncovered for use as a metal padand for connecting this electrode with others. In this example, thevoltage window of the planar supercapacitor electrode varies betweenabout 1 V and 2.5 V depending on the type of electrolyte used in theassembly of the cells. Aqueous electrolytes often result in electrodeswith about 1 V, whereas voltages as high as about 2.5 V may be obtainedwhen using tetraethyl ammonium tetrafluoroborate (TEABF₄) inacetonitrile.

Electrolytes herein may include, for example, aqueous, organic and ionicliquid-based electrolytes. An electrolyte may be liquid, solid or a gel.An ionic liquid may be hybridized with another solid component such as,for example, polymer or silica (e.g., fumed silica), to form a gel-likeelectrolyte (also “ionogel” herein). An aqueous electrolyte may behybridized with, for example, a polymer, to form a gel-like electrolyte(also “hydrogel” and “hydrogel-polymer” herein). An organic electrolytemay be hybridized with, for example, a polymer, to form a gel-likeelectrolyte. Examples of electrolytes may include, but are not limitedto, aqueous potassium hydroxide, hydrogel comprising poly(vinyl alcohol)(PVA)-H₂SO₄ or PVA-H₃PO₄, aqueous electrolyte of phosphoric acid(H₃PO₄), tetraethyl ammonium tetrafluoroborate (TEABF₄) dissolved inacetonitrile, 1-ethyl-3-methylimidazoliumtetrafluoroborate (EMIMBF₄),ionogel comprising fumed silica (e.g., fumed silica nano-powder) mixedwith an ionic liquid (e.g., 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide (BMIMNTf₂)), and the like. Suchelectrolytes may provide a range of voltage windows (e.g., at leastabout 0.5 V, 1 V, 2 V, 3 V, 4 V or more). For example, some ionogels(e.g., fumed silica nano-powder with the ionic liquid BMIMNTf₂) mayprovide a voltage window of about 2.5 V and some hydrogel-polymerelectrolytes may provide a voltage window of about 1 V.

The active material in the electrodes may comprise carbonaceous and/orother suitable materials. For example, the active material in theelectrodes may be carbon, which may be activated carbon, graphene,interconnected corrugated carbon-based network (ICCN), or anycombination thereof.

ICCN may comprise a plurality of expanded and interconnected carbonlayers. For the purpose of this disclosure, in certain embodiments, theterm “expanded,” referring to a plurality of carbon layers that areexpanded apart from one another, means that a portion of adjacent onesof the carbon layers are separated by at least about 2 nanometers (nm).In some embodiments, at least a portion of adjacent carbon layers areseparated by greater than or equal to about 2 nm, 3 nm, 4 nm, 5 nm, 6nm, 7 nm, 8 nm, 9 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm,45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95nm or 100 nm. In some embodiments, at least a portion of adjacent carbonlayers are separated by less than about 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8nm 9 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm,55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm or 100 nm.In some embodiments, at least a portion of adjacent carbon layers areseparated by between about 2 nm and 10 nm, 2 nm and 25 nm, 2 nm and 50nm, or 2 nm and 100 nm. Moreover, for the purpose of this disclosure, incertain embodiments, the plurality of carbon layers is also defined ashaving an electrical conductivity greater than about 0.1 siemens/meter(S/m). In some embodiments, each of the plurality of carbon layers is atwo-dimensional material with only one carbon atom of thickness. In someembodiments, each of the expanded and interconnected carbon layers maycomprise at least one, or a plurality of corrugated carbon sheets thatare each one atom thick.

ICCN has a combination of properties that include, for example, highsurface area and high electrical conductivity in an expandedinterconnected network of carbon layers. In some embodiments, theplurality of expanded and interconnected carbon layers has a surfacearea of greater than or equal to about 500 square meters per gram (m²/g)or 1000 m²/g. In one embodiment the plurality of expanded andinterconnected carbon layers has a surface area of greater than or equalto about 1400 m²/g. In other embodiments, the plurality of expanded andinterconnected carbon layers has a surface area of greater than or equalto about 1500 m²/g, 1750 m²/g or 2000 m²/g. In yet another embodiment,the surface area is about 1520 m²/g. In some embodiments, the pluralityof expanded and interconnected carbon layers has a surface area ofbetween about 100 m²/g and 1500 m²/g, 500 m²/g and 2000 m²/g, 1000 m²/gand 2500 m²/g, or 1500 m²/g and 2000 m²/g. The plurality of expanded andinterconnected carbon layers may have such surface areas in combinationwith one or more electrical conductivities (e.g., one or more electricalconductivities provided herein). Examples of such combinations areprovided elsewhere herein.

In one embodiment, the plurality of expanded and interconnected carbonlayers yields an electrical conductivity that is greater than or equalto about 1500 S/m. In another embodiment, the plurality of expanded andinterconnected carbon layers yields an electrical conductivity that isgreater than or equal to about 1600 S/m. In yet another embodiment, theplurality of expanded and interconnected carbon layers yields anelectrical conductivity of about 1650 S/m. In still another embodiment,the plurality of expanded and interconnected carbon layers yields anelectrical conductivity that is greater than or equal to about 1700 S/m.In yet one more embodiment, the plurality of expanded and interconnectedcarbon layers yields an electrical conductivity of about 1738 S/m. Insome embodiments, the plurality of expanded and interconnected carbonlayers yields an electrical conductivity of greater than or equal toabout 1800 S/m, 1900 S/m or 2000 S/m.

Moreover, in one embodiment, the plurality of expanded andinterconnected carbon layers yields an electrical conductivity that isgreater than about 1700 S/m and a surface area that is greater thanabout 1500 m²/g. In another embodiment, the plurality of expanded andinterconnected carbon layers yields an electrical conductivity of about1650 S/m and a surface area of about 1520 m²/g.

Two electrodes may be connected together in series with the uncoveredmetal part in between the two electrodes acting as a contact point. Thisassembly may produce twice as much voltage as the individual cell. Toincrease the voltage further, more electrodes may be connected togetherin series in which five electrodes are used to get voltages as high asabout 5 V when using aqueous electrolyte and 12.5 V when usingtetraethyl ammonium tetrafluoroborate (TEABF₄) in acetonitrile (e.g., upto about 5 V when using aqueous electrolyte and/or up to about 12.5 Vwhen using TEABF₄ in acetonitrile).

In principle, there may be no limit to the number of the electrodes thatmay be put together in series. Only the voltage required for theoperation of the unit may define the total number of electrodes neededfor the unit. For example, a unit having a voltage of about 180 V mayrequire 180 electrodes connected together to reach the target voltagewhen using water-based electrolytes and only 72 electrodes when usingtetraethyl ammonium tetrafluoroborate (TEABF₄) in acetonitrile.

Units consisting of a large number of electrodes may be divided intostrings consisting of a given number of electrodes (e.g., 12 cells)each, and additional metal contacts may be made around the edges.

A roll of an ultrathin layer of gold (100 nm) coated onto a sheet ofpolyimide (Kapton) is used as a model example for a current collector incells. Alternative current collectors include aluminum, copper, nickel,and stainless steel. Suitable current collectors may include variousconductive (e.g., metal) foils, and/or conductive coatings (e.g., onpolymer or other suitable sheet materials). In inset, the foil isaffixed onto a flat substrate such as, for example, a glass plate and ispartially covered by Kapton tape. The electrode slurry is then coatedonto the metallic foil using standard doctor blade technique.

In some embodiments, the film may be made directly on the substrate ofchoice (e.g., without being transferred). The substrate is insulatingand may be easily etched with a laser cutter. In this case a piece ofwood was used, but other substrates such as acrylic have also beensuccessfully used. The electrode material may be easily identified onthe sheet, the black material. The lines are uncovered metallic partsthat were obtained after the Kapton tape had been removed.

A laser cutter is used to etch (or pattern) the individual cells. Thefinal unit is shown. The size of the electrodes and the spacing betweenthem (i.e., the size of the dielectric) may be controlled by the lasertable.

A droplet of gel electrolyte is added to each individual electrode toenable the electrode to store charge. The unit may then be tested forits operating voltage, capacitance rating, internal resistance, cycle,and shelf life.

Provided in certain embodiments are stacked electrodes. Fabricatedstacked arrays of electrodes may be packaged using one package.

A supercapacitor electrode may comprise an aluminum foil coated with alayer of porous carbon (e.g., activated carbon). Such electrodes may beused in the assembly of high-voltage supercapacitors by stackingindividual electrodes in a vertical direction instead of the planarexpansion in the flat structure.

A sandwich structure is used in which two thin-film electrodes are puttogether face-to-face with polymer plastic separator and a few dropletsof the electrolyte to allow charge storage.

In this example, the individual electrodes are sealed from the sides sothat they do not leak the liquid electrolyte and to prevent shortcircuits with the other cells. Heat shrinking tubes with internalchemical resistance are the glue used to allow the assembly of severalelectrodes in vertical direction.

Single-sided coated electrodes and double-sided coated electrodes aremade simply by coating a layer of carbon on aluminum foil. Thedouble-sided electrode may be made in two steps in which the foil iscoated from one side, dried, and then coated from the other side. Insome embodiments, the foil may be coated on both sides simultaneously.

In this structure, the electrodes are stacked on top of each other. Thetotal number of electrodes varies depending on the required voltage.Metal tabs are attached to the bottom and top electrodes to allow forinternal connection to the positive and negative terminals. Plasticgaskets 18 are used to prevent short circuit between positive andnegative terminals.

A fully assembled high-voltage supercapacitor having stainless steel (orother suitable material) shims (discs) are used to give the unitphysical robustness (e.g., to afford the pressure made by the heatshrinking tubes during assembly). The electrodes in this example may be,for example, single-sided coated electrodes or double-sided coatedelectrodes as described elsewhere herein.

The electrode may comprise a high-density polyethylene (HDPE) insulatorin contact with a positive (electrode) terminal. The positive terminalin turn is in contact with a positive (electrode) plate. The positiveplate may comprise one or more active electrode materials, such as, forexample, graphene. The active electrode material may be provided on oneside of the positive plate. The positive plate may be positioned suchthat the side of the plate that comprises the graphene (or any otheractive material herein) faces a paper layer (e.g., downward(“side-down”)). On the other side of the paper layer, a negative(electrode) plate 6 is in contact with the paper layer. The negativeplate may comprise one or more active electrode materials, such as, forexample, graphene. The active electrode material may be provided on oneside of the negative plate. The negative plate 6 may be positioned suchthat the side of the plate that comprises the graphene (or any otheractive material herein) faces the paper layer (e.g., upward(“side-up”)). The active materials of the positive and/or negativeplates may be provided or fabricated, for example, as describedelsewhere herein (e.g., by coating). The other side of the negativeplate is covered or enclosed in electrode housing. The electrode housingmay be pre-formed. At least a portion of the layers of electrode may besaturated with electrode. For example, electrolyte saturation may existbetween all layers.

In some embodiments, the single electrode may have an outer diameter ofabout 20 millimeters (mm). An electrode housing may enclose the edges ofthe electrode top to bottom (i.e., across all layers). The electrodehousing may be formed. At the top of the cell, the electrode housing mayform a flange over the edge of the HDPE insulator. At the bottom of thecell, the electrode housing may form a flange over the edge of theelectrode housing.

The electrode stack may comprise, for example, a plurality of the cells.The protruding electrode terminals of individual electrodes allow theelectrodes to be electrically interconnected.

Aspects of the disclosure may be used in combination. For example, twoor more planar expansions may be stacked in a configuration adapting oneor more features of the stacks mentioned above. In another example, oneor more components (e.g., paper layer, separator or housing components)of the stacks mentioned above may be used in another stackingconfiguration.

Systems and methods of the disclosure may be adapted to other activematerials. For example, during fabrication of planar arrays ofelectrodes (e.g., by masking, coating, drying and patterningelectrodes), two-step electrode coating (and other fabrication stepssuch as, for example, masking) may be used to fabricate adjacentelectrodes comprising different (or asymmetric) active materials. Suchembodiments may enable, for example, fabrication of batteries comprisinga plurality of interconnected battery cells, or other devices (e.g.,photovoltaics, thermoelectrics or fuel cells) comprising electrodes withdifferent (or asymmetric) electrodes.

A plurality of electrodes may be interconnected to form supercapacitorsand/or other devices (e.g., batteries, various types of capacitors,etc.). For example, at least about 2, 5, 10, 20, 30, 40, 50, 75, 100,125, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 900, 1000, 1500,2000 or more electrodes may be interconnected (e.g., in series). In someembodiments, between about 50 and 300 electrodes may be interconnected.

A high-voltage device (e.g., high-voltage supercapacitor) may have avoltage of greater than or equal to about 5 V, 10 V, 15 V, 20 V, 30 V,40 V, 50 V, 60 V, 70 V, 80 V, 90 V, 100 V, 110 V, 120 V, 130 V, 140 V,150 V, 160 V, 170 V, 180 V, 190 V, 200 V, 210 V, 220 V, 230 V, 240 V,250 V, 260 V, 270 V, 280 V, 290 V, 300 V, 310 V, 320 V, 330 V, 340 V,350 V, 360 V, 370 V, 380 V, 390 V, 400 V, 410 V, 420 V, 430 V, 440 V,450 V, 460 V, 470 V, 480 V, 490 V, 500 V, 510 V, 520 V, 530 V, 540 V,550 V, 560 V, 570 V, 580 V, 590 V, 600 V, 650 V, 700 V, 750 V, 800 V,850 V, 900 V, 950 V or 1000 V. A high-voltage device (e.g., high-voltagesupercapacitor) may have a voltage of less than about 10 V, 15 V, 20 V,30 V, 40 V, 50 V, 60 V, 70 V, 80 V, 90 V, 100 V, 110 V, 120 V, 130 V,140 V, 150 V, 160 V, 170 V, 180 V, 190 V, 200 V, 210 V, 220 V, 230 V,240 V, 250 V, 260 V, 270 V, 280 V, 290 V, 300 V, 310 V, 320 V, 330 V,340 V, 350 V, 360 V, 370 V, 380 V, 390 V, 400 V, 410 V, 420 V, 430 V,440 V, 450 V, 460 V, 470 V, 480 V, 490 V, 500 V, 510 V, 520 V, 530 V,540 V, 550 V, 560 V, 570 V, 580 V, 590 V, 600 V, 650 V, 700 V, 750 V,800 V, 850 V, 900 V, 950 V or 1000 V. In some embodiments, ahigh-voltage device (e.g., high-voltage supercapacitor) may have avoltage of at least about 100 V. In some embodiments, a high-voltagedevice (e.g., high-voltage supercapacitor) may have a voltage of atleast about 180 V. In some embodiments, a high-voltage device (e.g.,high-voltage supercapacitor) may have a voltage of up to about 540 V. Insome embodiments, a high-voltage device (e.g., high-voltagesupercapacitor) may have a voltage of between about 100 V and 540 V, 180and 540 V, 100 V and 200 V, 100 V and 300 V, 180 V and 300 V, 100 V and400 V, 180 V and 400 V, 100 V and 500 V, 180 V and 500 V, 100 V and 600V, 180 V and 600 V, 100 V and 700 V, or 180 V and 700 V.

Those skilled in the art will recognize improvements and modificationsto the present disclosure. All such improvements and modifications areconsidered within the scope of the concepts disclosed herein.

What is claimed is:
 1. An energy storage device comprising: an array ofelectrodes, wherein each electrode comprises a current collector; and anactive material directly on a portion of a first surface of the currentcollector, wherein the active material comprises two or more expandedand interconnected carbon layers, wherein at least one of the carbonlayers is corrugated and one atom thick.
 2. The energy storage device ofclaim 1, further comprising the active material directly on a portion ofa second surface of the current collector.
 3. The energy storage deviceof claim 1, wherein each electrode in the array of electrodes isseparated from a subsequent electrode by a gap.
 4. The energy storagedevice of claim 1, wherein the current collector comprises a metal film,a polymeric film, or any combination thereof, wherein the metal filmcomprises silver, copper, gold, aluminum, calcium, tungsten, zinc,brass, bronze, nickel, lithium, iron, platinum, tin, carbon steel, lead,titanium, stainless steel, mercury, chromium, gallium arsenide, or anycombination thereof, and wherein the polymeric film comprisespolyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene,polyacetylene, poly p-phenylene vinylene, polypyrrole, polycarbazole,polyindole, polyazepinem, polyaniline, polythiophene, poly3,4-ethylenedioxythiophene, poly p-phenylene sulfide, polyacetylene, orany combination thereof.
 5. The energy storage device of claim 1,wherein a portion of the carbon layers is separated by a distance ofabout 25 nm to about 150 nm.
 6. The energy storage device of claim 1,wherein the active material comprises carbon, activated carbon,graphene, polyaniline, polythiophene, an interconnected corrugatedcarbon-based network (ICCN), or any combination thereof.
 7. The energystorage device of claim 1, wherein the active material has a specificsurface area of from about 250 meters squared per gram to about 3,500meters squared per gram.
 8. The energy storage device of claim 1,wherein the active material has a conductivity of from about 750siemens/meter to about 3,000 siemens/meter.
 9. The energy storage deviceof claim 1, wherein the active material has a surface density of atleast about 250 m²/g.
 10. The energy storage device of claim 1, furthercomprising an electrolyte.
 11. The energy storage device of claim 10,wherein the electrolyte is a liquid, a solid, a gel, or any combinationthereof.
 12. The energy storage device of claim 10, wherein theelectrolyte comprises a polymer, silica, fumed silica, fumed silicanano-powder, 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, phosphoric acid, tetraethyl ammoniumtetrafluoroborate (TEABF₄), acetonitrile,1-ethyl-3-methylimidazoliumtetrafluoroborate, ethanolammonium nitrate, adicarboxylate, a prostaglandin, adenosine monophosphate, guanosinemonophosphate, a p-aminohippurate, polysiloxane, polyphosphazene,potassium hydroxide, polyvinyl alcohol, or any combination thereof. 13.The energy storage device of claim 10, wherein the number of electrodesis 5, provided that a voltage potential produced across the array ofelectrodes is from 6 V to 24 V.
 14. The energy storage device of claim10, wherein the number of electrodes is 72, provided that a voltagepotential produced across the array of electrodes is from 100 V to 360V.
 15. The energy storage device of claim 10, wherein the number ofelectrodes is 180, provided that a voltage potential produced across thearray of electrodes is from 100 V to 360 V.
 16. The energy storagedevice of claim 1, wherein the array of electrodes is a two-dimensionalplanar array of electrodes.
 17. The energy storage device of claim 1,wherein the array of electrodes is a stacked array of electrodes. 18.The energy storage device of claim 17, further comprising at least oneor more of a separator and a support between a pair of adjacentelectrodes.
 19. The energy storage device of claim 1, wherein theelectrode is a double-sided electrode.
 20. The energy storage device ofclaim 1, wherein the electrode is a single-sided electrode.